Unsaturated ether



United States Patent Ofifice 3,297,707 Patented Jan. 10, 1967 3,297,767 UNSATURATED ETHER Theodor Leidig and Giitz Wustmann, Holzminden, Germany, assignors to Haarmann & Reimer G.m.b.H., Holzminden, Germany, a corporation of Germany No Drawing. Filed June 11, 1963, Ser. No. 286,953 Claims priority, application Germany, June 12., 1962, H 46,047 1 Claim. (Cl. 260614) in which R and R represent alkly radicals with 4-9 carbon atoms. The following compounds are mentioned as examples:

Bis-S-methyl-hex-Z-en-1-ol ether,

B.P 119-124 C.; D 0.820; n 1.4468,

Bis-hept-Z-en-l-ol ether (smells like orange peel),

B.P. 127131 C.; D 0.826; r1 1.4500,

Bis-4-methyl-hept-2-en-l-ol ether (smell: fatty, like green core),

B.P. 142148 C.; D 0.828; r1 1.4525,

Bis-oct-Z-en-l-ol ether (has a strong odour of hempseed),

B.P 127133 C.; D 0.829; r1 1.4525,

Bis-non-Z-en-l-ol ether (fragrance of unused linen),

Bis-4-ethyl-oct-2-en-l-ol ether (smell of egg shell and B.P 149-156" C.; D 0.831; 11 1.4533,

Bisdec-2-en-l-ol ether (the smell reminiscent of fresh lard),

B.P 163168 C.;DE 0.826; 11 1.4557,

Bis-undec-Z-en-l-ol ether (smell: waxy, like blown-out candle),

B.P 196 203 C.; D 0.832; r1 1.4563,

Bis-dodec-Z-en-l-ol ether (smell: slightly of peach, like blown-out candle),

B.P 216-22l C.;DE": 0.839; n 1.4583.

The series has a culmination point in the bis-non-2- en-l-ol-ether, which has the characteristic odour of fresh and unused linen. When added to used articles made of linen, nettle cloth, cotton and the like, and after the washing thereof, it imparts the odour of brand-new, unworn linen, as sold in the shops. Once an article has been impregnated therewith, it keeps this fresh fragrance for months on end on being kept in the open air.

The compounds used according to the invention can for example be produced by heating l-halogen-Z-ene hydrocarbons, containing 712 carbon atoms in the molecule, in the presence of alkalis and in the presence of tertiary butanol. Examples of the l-halogen-Z-ene hydrocarbons are 1-chloro-2-octene, l-chloro-Z-nonene or 1-chloro-2-dodecene. The chlorine and bromine compounds are generally the most suitable as halogen compounds. Caustic potash or caustic soda can for example be used as alkalis. The reaction can for example be effected by gradually adding the unsaturated halogenated hydrocarbon to the mixture of alkali and tertiary butanol.

The new odorous substances can be used in the manner which is usual for such substances, optionally in admixture with other odorous components. When bis-non- 2-en-1-ol ether is used as an odorous substance for linen, it is expedient to use aqueous emulsions which can also contain other constituents, e.g. synthetic resin dispersions. The new odorous compounds are used in usual amounts according to taste and the necessary amounts can be easily determined by experiments.

Example 1 A stable emulsion is prepared, as indicated below, from bis-non-2-en-1-ol ether by adding an emulsifier and a synthetic resin dispersion:

Parts by wt.

Synthetic resin dispersion 500 Emulsifier 25 Water 250 Bis-non-Z-en-l-ol ether 225 The bis-non-2en-1-ol ether was prepared in the following way:

A solution of n-hexyl magnesium chloride is produced from 240 g. of magnesium and 5 litres of diethyl ether with 1200 g. of n-hexyl chloride. The content of Mgcompound in the solution is titrated and 0.8 Inol=45 g. of freshly distilled acrolein per 1 mol'of Mg-compound is slowly added at 0 C. After being left to stand overnight, the substance is decomposed with ice-cold dilute acetic acid, washed until neutral and distilled in vacuo after evaporating the ether. 825 g.=78% of non-l-en-3-ol is obtained at 88-92 C./1O 111111., with the following constants: D 0.836; 11 1.4404.

142 g. of non-1-en-3-ol and 1 litre of concentrated hydrochloric acid are mixed and thoroughly stirred for 8 hours at 70 C. The 1-chloro-2-nonene which is formed is extracted by shaking with methylene chloride, washed neutral with sodium bicarbonate solution and distilled after evaporating the methylene chloride.

B.P. 7179 C.; D 0.878; n 1.4483%; Cl, 20.52

(theoretical 22.05

Yield: 148 g.=92.5% of the theoretical,

Residue: 16 g.

Fraction I: 64 C./5 mm.-161 C./5 mm. 74 g. Fraction II: 161 C./5 [URL-166 C./5mm. 77 g.

Fraction I still contains 13.4% of Cl and can be used again after the 1-chloro-2-nonene has been removed by fractionation.

Fraction II is bis-non-2-en-1-ol-ether. g.=5 8%.

The other compounds used according to the invention can be obtained in a corresponding manner.

Yield: 77

Example 2 (a) From bis-non-2-en-1-ol ether and with the aid of an emulsifier mixture, a clear solution is produced which is stable:

Parts by wt. Bis-non-2-en-1-ol-ether 200 Emulsifier 800 (b) The products described in Examples 1 and 2a can either be applied to the garments by a dipping process or spraying process. Using the dipping process, about -10 g. are added per litre of bath liquid.

Using a spraying process, the textiles can be sprayed with an aqueous dispersion of these products, which contain about 50 g. per litre of water.

It is expedient for this purpose to use a spray pistol with a very fine nozzle, so that a relatively dry mist is deposited on the textiles.

Example 3 Example 4 Instead of the pure bis-non-Z-en-l-ol-ether, it is also possible in Examples 1, 2a and 3 to use compositions with a varying content of bis-non-Z-en-l-ol-ether, e.g.:

Percent Bis-non-2-en-1-ol-ether 10 Formosa citronella oil 20 Safrol 10 Oil of lavender 58 Ambrette seed oil 2 4 Example 5 The following method of application is mentioned as an example for the use of bis-oct-2-en-1-ol-ether:

Part by wt.

Bis-oct-Z-en-l-ol-ether 200 Emulsifier 800 Material which is processed into binding threads, ropes or cords is treated with this solution by the dipping or spraying process. The finished goods then have the smell of true hemp tow.

We claim:

Compound of the formula:

References Cited by the Examiner UNITED STATES PATENTS 2,042,219 5/1936 Groll et al.

FOREIGN PATENTS 1,074,031 1/1960 Germany.

OTHER REFERENCES Prevost, C.: Bull. Soc. Chim. 8 pp. 89-100 (1941).

LEON ZITVER, Primary Examiner.

H. T. MARS, Assistant Examiner. 

